PL91692B1 - - Google Patents

Description

Patent description was published: June 30, 1977 91692 MKP AOln 9/22 C07d 55/10 Int. Cl.2 A01N 9/22 C07D 253/02 READING ROOM Patent Office PiUJii) IZ5W »'^:«! Li ^ * «i Inventor: The holder of the patent: Bayer Aktiengesellsehaft, Leverkusen (Republi¬ ka 'Federal Republic of Germany) Herbicide 2 The invention relates to a herbicide containing as active substances new 3,4-double hydrogen-1,2,4-triazines. The method of output is already known for the formation of 1 ^ -dihydrogen-1 ^-triazines, e.g. 6-ben- zyl-3-mercapto-1,6-dihydro-1,2,4-triazin-5-one, by reduction with sodium amalgam from 6-benzyl-3- -merkapto-1,2,4-triazinone-5 according to scheme 1) (comp. Bulletin de la Sociste chimiaue de la France 11, (1944), 273).

Moreover, it is known that containing nitrogen, six the chlorine heterocyclic rings can be re¬ dilute with sodium borohydride in aqueous solution or alcoholic, and at least one of the nitrogen rings remains intact completely reduced, while the carbonyl- wa remains intact (diagram showing symbol the R pain in the formulas is N (CHS) 2, Cl, C2H & CH (CHa) 2, CF8, OCH3 and scheme 3) (comp. Description United States Patent No. 3271396 and Helvetica Chimca Acta 50, 1492-1498 (1967) and ibid. 51, 1029-1036 (1968). ' It has been found that new 3,4-dihydro-1,2,4-tria- s of formula I in which R 1 is the radical al alkyl or cycloalkyl, R2 is a methyl radical or amino, alkylidenamino, methyl β-hydroxyethyl-amino, 2-furyl-methyl- back of the imine and optionally substituted aryl alkylamino and R3 is alkyl or an optionally substituted aryl radical, listed has a very good herbicidal effect.

The new 3,4-dihydro-1,2,4-triazines are obtained with 1,2,4-triazinone-5 of formula 2, wherein R1, R2 and R3 have the above meanings, by reduction sodium borohydride in the presence of polar solutions of solvents at a temperature between -10 and + 25 ° C.

From the active substances of the agent according to the invention, you can list, for example: 3-methyl-4-amino-5-hydroxy-6-phenyl-3,4-dihydroxy- doro-1,2,4-triazine, 3-methyl-4-methyl-5-hydroxy-6-phenyl-3,4-di- hydro-1,2,4-triazyine, 3-isopropyl-4-methyl-5-hydroxy-6-phenyl-3,4- - dihydrogen-1,2,4-triazine, 3-methyl-4-amino-5-hydroxy-6-tertiary butyl- -3,4-dihydro-1,2,4-triazines, 3-ethyl-4-amino-5-hydroxy-6-phenyl-3,4-dihydroxy- doro-1,2,4-triazine, 3-isopropyl-4-amino-5-hydroxy-6-phenyl-3,4- - dihydrogen-1,2,4-triazine, 3-methyl-4-methylamino-5-hydroxy-6-phenyl-3,4- - dihydrogen-1,2,4-triazine, 3-methyl-4-amino-5-hydroxy-6-p-methylphenyl- -3,4-dihydro-1,2,4-triazines, 3-methyl-4-amino-5-hydroxy-6- (2 ', 4'-dimethoxy- phenyl) -3,4-dihydro-1,2,4-triazine, 3-methyl-4-amino-5-hydroxy-6- (4'-chlarophenyl) - -3,4-dihydro-1,2,4-triazine.

New 3,4-dihydroTo-1,2,4-forming triazines the active substances of the agent according to the invention are 916923 91692 4 I have good herbicidal properties and may know lezc application for weed control.

Weeds, in the broadest sense, are all plants, growing in places where they are not disturbed given. It depends on the amount of active substance used, 5 whether the measure according to the invention works as total or a selective herbicide.

The agent according to the invention comprises a substance The active ingredients of the formula I can be used, for example, in ratio to the following plants such as: hot-10 czyca (Sinapis), peppercorn (Lepidium), shrimp (Galium), nest (Stellaria), chamomile (Matri- caria), yellowberry (Galinsoga), quinoa (Chenopodium), nettle (Urtica), old man (Senecio), timothy (Phleum), panicle (Poa), fescue (Festuca), 15 manneczka (Eleusine), trichinella (Setaria), ryegrass (Dolium), stoklosa (Bromus), weed (Echino- chloa), millet (Panicum).

The active ingredients of the agent according to the invention affect plant growth very strongly, however 20 in various ways so that they can be used as a series lax herbicides. Special advantages they show as selective herbicides for cotton, maize and cereals.

At higher concentrations, they can be used as 2s total herbicides.

The agent according to the invention may be dispersible in the usual forms such as solutions, emulsions sieves, suspensions, powders and granules.

They are produced in a known manner, for example by change mixing active substances with fillers, a so the liquid solvents that are present under the pressure of liquefied and / or solid gases carriers, using in this case means surfactants, and therefore emulsifiers distracting and / or distracting.

In case of using water as a filler organic solvents, for example, can be used niki as auxiliary measures. As a liquid . solvents come into consideration: aromatic compounds ne, such as xylene, toluene, benzene or alkyl naphthalene chlorinated aromatic or chlorinated compounds aliphatic hydrocarbons such as chlorobenzene, chloro ethylene or methylene chloride, aliphatic carbon hydrogens like cyclohexane or paraffins, e.g. fractions petroleum, alcohols like butanol or glycol like 4B also their ethers and esters, ketones like acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexa non, strongly polar solvents such as dimethyl lformamide and dimethylsulfoxide as well water. As liquefied gas fillers or no- 50 Carbon dioxide is defined as such liquids which, at the temperature at normal pressure and under normal pressure gaseous puja, e.g. liquid propellants in an aerosol, e.g. halogenated hydrocarbons, e.g. freon.

Natural M flour is used as permanent carriers stones, such as kaolins, aluminum oxides, talc, chalk quartz, attapulgite, montmorillonite, or earth diatomaceous, and synthetic stone flour like highly dispersible silicic acid ia, alumina and silicates. As emulsifiers - 60 where nonionic and anionic emulsifiers are used, such as polyhydroxyethylene fatty acid esters polyhydroxyethylene ethers of fatty alcohols e.g. ether, polyhydroxyethylene alcohols fatty acids, e.g. polyglycol alkylaryl ether, 65 alkyl sulfonates, alkyl sulfates and sulfonates aryls. They are used as dispersants e.g. lignin, sulfite lugs and methylcellulose.

The active ingredients of the agent according to the invention can be it appears in the final form as a mixture ny with other known active substances.

Final forms usually contain between 0.1 - 95% by weight of active ingredient, mostly between 0.5 and 90P / <* weight.

The active ingredients of the agent according to the invention can be to be used as prepared from them consumables, such as a ready-to-use solution rice, emulsions, suspensions, powders, pastes and granules.

They are normally used e.g. by pouring, spraying skirting, in the form of a mist, sprinkling, spraying.

Application is possible both after and before getting up.

The amount of active ingredient used may vary within wide limits. It depends essentially on the type of expected effect. Overall a hundred Valuable amounts vary between 0.1 and 20 kg per 1 ha, usually between 0.2 and 15 kg / ha.

The agent according to the invention also shows fungicidal activity, in particular against grain diseases such as rust.

It should be stated as surprising that when the preparation of compounds of formula I by reaction of the compound of formula II with sodium borohydride is the selective reduction of the carbonyl group in in the ring of 1,2,4-triazin-5, the second the hydrogen atom does not attach to C-5, but to C-3.

Compounds of formula I are obtained with high cleanliness and with great efficiency. In the way the preparation of compounds of formula 1 can be used cheap, non-poisonous solvents and they are not horse Necessary large equipment expenditures.

If used as starting material 3-methyl-4-methylamino-6-phenyl-1,2,4-triazin-one- -5, the course of the reaction is presented in Scheme 4.

Output products are generally defined formula 2. In formula 2, preferably R1 is a straight or branched alkyl radical zinced, containing 1-6, especially 1-4 atoms carbon or a cycloalkyl radical containing 3-6 especially 3 carbon atoms. In formula II, R2 is has preferably CH8-, NH2-, NHCH8-, and -NHCH2CH2OH, 2-fiurylmethylamino or optionally methyl-substituted benzine amino, further alkylidene amino, with whereby the alkylidene moiety preferably comprises 3-8, especially 3-6 carbon atoms.

In formula 2, R3 is preferably the radical al keel chain with a straight or branched chain, incl containing 1-4 carbon atoms or possibly, a monosubstituted or multi-substituted aryl radical, e.g. containing 6-10, especially 6 carbon atoms. Pod the substituents are usually: an alkyl radical containing hardy 1-4 carbon atoms, halogen, especially chlorine, bromine, fluorine, alkyl halides with 1-2 atoms carbon and 2 to 5 halogen atoms, especially fluorine, nitro group or phenoxy group.

Usable 1,2,4-triazin-ones- -5 of formula 2 in which R2 is not substituted Alkylidene amine, the description of p German Tentative of DOS No. 2107 757 and 2138 031) .91692 Compounds of formula II in which R2 is tgr pe alkylidene amine are discussed in the description of pa German Tentate DOS 2238206. 1,2,4-triazin-ones-5- Formula II in which R2 is alkylide noamine, is made from the known 4-amino-SH- -1,2,4-triazin-5-5 of the formula 3, wherein R 1 i R3 have the meaning given above, in reaction with carbonyl compounds of formula 4 wherein R4 is a hydrogen atom or an alkyl radical, R5 represents an alkyl radical. The reactions are carried out in given case in the presence of inert dissolution an organic solvent, for example a hydrocarbon, such as petrol zen, an ether such as dioxane or tetrahydrofuran and possibly in the presence of an acid catalyst, for example a Lewis acid such as ferric chloride or tin acid or an organic acid such as p-toluenesulpho new, at a temperature of 0-120 ° C.

Likewise, they can be obtained Compounds defined by formulas 2b and 2c, with temperature melting points of 99 ° C and 136 ° C, respectively.

As exemplary starting materials, use the formula 2 can be mentioned: 3-methyl-4-amino-III-order. butyl-1,2,4-triazine- -on-5, 3-III-row butyl-4-amino-6-III-order. butyl-1,2,4- -triazin-on-5, 3-isopropyl-4-amino-6-III-order. butyl-1,2,4-tria- zyn-on-5, 3-methyl-4-amino-6-phenyl-1,2,4-triazin-one-5, 3-isopropyl-4-amino-6-phenyl-1,2,4-triazin-one-5, 3-methyl-4-amino-6-p-methylphenyl-1,2,4-triazin- -on-5, 3-methyl-4-amino-6-o-methylphenyl-1,2,4-triazine- -on-5, 3-methyl-4-amino-6-α-trifluoromethylphenyl-1,2,4- -triazin-on-5, 3-methyl-4-amino-6-o-trifluoromethylphenyl-1,2,4- -triazin-on-5, 3-methyl-4-aniino-6- (2'-methyl-4'-chlorophenyl) - -1,2,4-triazin-on-5, 3-methyl-4-methylamino-6-phenyl-1,2,4-triazine- -on-5, 3-methyl-4-benzylamino-6-phenyl-1,2,4-triazine- -on-5, 3-methyl-4-isopropylideneamki-6-phenyl-1,2,4- -triazin-on-5, 3-methyl-4-isopropylideneamino-6- (2'-methylphen- lo) -1,2,4-triazin-one-5, 3-methyl-4-methylamino-6-III-order. butyl-1,2,4- triazin-on-5, 3-methyl-4-methyl-6-tertiary butyl-1,2,4-triazine- -oh-5, 3-methyl-4-methyl-6-phenyl-1,2,4-triazin-one-5, 3-isopropyl-4-methyl-6-phenyl-1,2,4-triazin-one-5, Everything is considered as diluents polar organic solvents. Usually they include: ethers such as dioxane and tetrahydro furan or alcohols such as methanol and ethanol.

Reactions are carried out at temperatures from -10 to +25 ° C, preferably at a temperature of -5 to + 10 ° C.

Reactions can be carried out under normal and so- with increased pressure. In general it is operated at a pressure of 1-1.5 atm, preferably 1-1.2 atm.

Conduct the process on 1 mole of 1,2,4-triazin-5 for formula II, 1.2 moles of sodium borohydride are used.

Further exceeding the stoichiometric ratios it does not significantly improve the performance.

In order to isolate the active substances, Fr. In formula 1, the solvent is distilled off under reduced pressure to almost dry, and constancy is driven by water. The sediment drains off and that's fine washed with warm water. 3,4-dihydro-triazines fall out of the solution as a rule as fine steel powder and need not be crystalline anymore licked.

Herbicidal effectiveness of active substances The means according to the invention are shown as follows jace examples.

Example I. Post-entry test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of an alkylaryl ether it polyglycol.

In order to prepare the right mixture of the active ingredient, 1 part by weight of the active ingredient is mixed active state with the specified amount of solvent, adds the specified amount of emulsifier and dilutes the concentrate water centrate to the desired concentration.

The active ingredient mixture is sprayed on to the ground test saliva 5-15 cm high in this manner Please use the amount of the substance specified in the table per unit area. Depending on the the concentration of the mass to be sprayed the amount of water used is 1000-2000 l / ha.

After three weeks, the degree of the ear is determined plant roots and are marked with identification numbers their 0-5, which have the following meanings. 0 - no operation, 1 - single, weak burned spots 2 - visible leaves damage, 3 - single leaves and fragments of stems parts I am dead, 4 - plant partially destroyed, - the plant has completely died.

Active substances, amounts used and results before are listed in Table 1 below. 40 45 5,091,692 Table I Post-entry test Substance open The union of Fr. formula 5 The union of Fr. formula 6 The union of Fr. formula 7 Consumption of sub of activities kg / ha 2 1 0.5 0.25 2 1 0.5 0.25 2 1 0.5 0.25 Echi- Well- chloa 4 4 4 4- ^ 5 4 ^ 5 4 4-5 3 Che- nopo- diuim 4-5 4 4-5 Sina- writing , 5 Ga- lin- isoga 3 2 . 4 Stel- laria 4-6 3 4-5 4 .5 Uiti- ca Ma- trica- Yee 4 4 3 Deu- cus 3 3 3 3 Oat 4 ^ 5 4 3 2 4 4 2 1 3 3 Ba¬ wel¬ on 4 ^ 5 2 1 1 3 2 0 4 3 First nothing 4 2 2 1 3 3 3 1 4 3 3 2 Fa¬ sole 4-5 4-5 3 3 4-5 4-5 2 4-5 4 Example II. Pre-entry test » Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of an alkylaryl ether it polyglycol In order to prepare the right mixture, so of the active ingredient, 1 part by weight of the active ingredient is mixed active state with the specified amount of solvent, adds the specified amount of emulsifier and dilutes the concentrate water centrate to the desired concentration.

The seeds of the test plants are sown in the normal range the substrate and the mixture is poured over after 24 hours active substance. At the same time, the amount of water per unit The surface area remains on a permanent basis dude. The concentration of the active substance in the mixture does not play a role, only the amount of ej and active per unit area. After three weeks, the degree of damage to the test plants is defined by the distinguishing numbers 0-5, which have the following meanings: 0 - no operation, 1 - slight damage or growth retardation, 2 - pronounced damage or inhibition growth, 3 - minor damage and insufficient development or rising in 50p / o, 4 - plants partially destroyed after germination ne or ascent in 25 w / o, - the plants have died completely or are not grown scia.

Active substances, amounts used and results are reported no in Table II below: Table II Pre-entry test Substance open Relationship formula 5 Relationship formula 6 Relationship formula 7 Consumption of substances active kg / ha 2.5 1.25 2.5 1.25 2.5 1.25 Sina- writing 4 3 4 3 Echi- Well- chloa 4-5 4 ^ 5 Heno- pe- dium 4 ^ 5 LrO- lium 4 4 Stel- larda Ma- trica- ria 4-6 Oat 4 3 3 2 4 3 2 0 4- ^ 5 4- ^ 5 Ba¬ wel¬ on 3 2 2 1 4 3 3 1 4-5 4 4 First nothing 3 2 2 2 4 3 3 3 4 4 4 4 Buckwheat custom czaj on 4 ^ 5 3 2 4-5 4 4 1 4 ^ 5 4 ^ 5 4 3 ^ Ku¬ chickens yeah 2 2 1 0 2 2 2 1 4 4 3 391692 9 Example III. Obtaining the compound of the formula rze 6. 108 g {0.5 mol) 3-methyl-4-methyleneamino-6-phe- nyl-1,2,4-triazine-one-5 is suspended in 1 liter of meta nolu. 19.0 g are added in portions to this suspension (0.5 mol) sodium borohydride, while stirring and cooling external reaction medium to 0-10 ° C. After the break At the end of the addition, the mixture is stirred for 4 hours at a temperature temperature 0-5 ° C, then 8 more hours at room temperature. A transparent, a yellow solution that frees itself from solvents ka under reduced pressure. The remainder of the water is released, the precipitate is filtered off rinsed thoroughly with water and dried. After drying 90 g (83% of theory) are obtained (5-hydroxy-3-methyl-4-methylamino-6-phenyl-3,4- - 1,2,4-triazine -dihydrogen, m.p. temperature 91 ° C.

Example IV. Preparation of the compound of formula rze 8. 21.5 g (0.1 mol) of 3-ethyl-4-methyl-6-phenyl-1,2,4- triazin-one-5 is suspended in 200 ml of methanol and mixed with water the ice-cooling time is added in portions of 4.6 g (0.12 mol) sodium borohydride. After a few hours stirring while cooling with ice is allowed temperature rise to 20 ° C and stirring is continued 8 hours at room temperature. From risen the solution is partially distilled off the solvent under reduced pressure, the oily residue remained Water is added to it and the sediment is sucked away well it is washed with water and dried. 18.4 g are obtained (85% of theoretical yield (3-ethyl-5-hydroxy- ii -4-methyl-6-phenyl-3,4-dihydro-1,2,4-triazine o mp 122 ° C.

In the same way as in examples III and IV has been obtained, for example in Table III relationships.

Example XXVII. Receipt of a relationship, according to the formula 2a, 10.8 g (0.05 mol) of 3-ethyl- -4-amino-6-phenyl-5H-1,2,4-triazin-5-(known from of the German advertisement description DOS 2138 031) in 250 ml of acetone and after adding 0.1 g of acid The su p-toluenesulfonic acid is heated during 1 hours to boiling under reflux. Chap the product is sipped hot, then distilled part of the solvent is eaten up, and the rest is caught gives 20 to 50 ml of isopropanol. The obtained crystalline a large precipitate is filtered off and washed with ether. Received This results in 10.9 g {85% yield theory) 3-ethyl-4-propylideneamino-6-phenyl- -5H-1,2,4-triazin-one-5, m.p. 146 ° C. ii

Claims (3)

Patent claim A herbicide, characterized in that it contains as active ingredient at least one 3,4-dihydro-1,2,4-triazines of the formula I in which a methyl radical or an amino group, alkylideneamino, methylamino, and -hydroxyethylamino, 2-furylmethylamino and optionally substituted arylalkylamino, and R3 is alkyl or an optionally substituted aryl radical, and known carriers and / or surfactants. Table III Preparation of compounds of general formula 1 Example No. V VI VII VIII IX X XI XII XIII XIV XV XVI XVII XVIII * XIX XX XXI XXIII XXIII xxiv xxv XXVI R1 CHS C2H5 C2H5 C4H9 C ^ Hu C2H5 H C2H5 CH (CH3) 2 C2H5 C2H5 C * H5 C6H18 CH8 C2H5 CH «OH3 C2H5 C * H5 CsH5 CH8 formula 15 R2 NH2 NH2 NH2 NH2 NH2 NH2 NH2 NH2 NH2 NH2 NHCH8 NHCH3 NHCH8 NHCH8 NHCH2CH2CH formula 11 N = C (CH8) 2 N = C (CH8) * N = aCH3) 2 NH2 formula 16 NH2 R3 formula 9 formula 9 formula 10 formula 9 formula 12 C (CH8) 8 C {CH8) 8 C (CH3) 8 formula 13 C (CH8) 8 formula 9 formula 9 formula 14 pattern 9 pattern 9 pattern 9 pattern 9 pattern 10 pattern 17 pattern 9 pattern 9 Melting point 135 101 108 120 95 92 58—61 114 183 145 91 140 96 134 126 119 147 100 114 408 79 175—17791692 OH * NR * "n * nAr1 HN — R * Formula 1 Ns ^ R1 Formula 2 V V- ^ Sl-N = c (pH ^ 2 '2n5 Formula 2a OH' 'C ^ SI) | -NH-CH5 fc C-CH3' * H Formula 6 OH i. * H Formula 7 OH / A- ^ MN = C (CH3) 2 Formula 2b NN = C (CH3) 2 F ^ C rV% 2H5 Formula 2c H Formula 8 Formula 8 Formula 10 o- Formula 9 NHCH2 \ _y CH3 Formula 11 N-NH, sA1 'Formula 3 0 = CV Formula A / F \ CL Formula 12 ao Formula 13 OH and C * S} I-NH ~ CH3 % A ~ HC2H5 Formula 5 K), -0 Formula 14 Formula 1591692 NHCH iii 2 Formula 16 P- 0CH3 Hzor 17 K 9 ^ An-H h9 Na / KgO { 3. -CH2y ^ N_H N ^^ - SH HNn ^ SH Scheme f ON ST \ NaBH ^ / MeOH scheme 291692 C6H5 NaBH4 / H2 (yO> 1nNaOH 6H5 Scheme 3 NaBH, OH N ^ N-NHCH, H Scheme A READING ROOM Pallet - hWIll lBmp «Wli '(| tli ¦; --¦ LZG Zd Nr 2 - 554/77 100 items ^ 4 Price *